CN117986563B - Porous composite metal catalyst for polyether synthesis and preparation method thereof - Google Patents
Porous composite metal catalyst for polyether synthesis and preparation method thereof Download PDFInfo
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 41
- 239000002184 metal Substances 0.000 title claims abstract description 41
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- 238000002360 preparation method Methods 0.000 title abstract description 15
- 238000001308 synthesis method Methods 0.000 title description 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 25
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- QSJXEFYPDANLFS-UHFFFAOYSA-N Diacetyl Chemical group CC(=O)C(C)=O QSJXEFYPDANLFS-UHFFFAOYSA-N 0.000 claims description 22
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- 239000003446 ligand Substances 0.000 claims description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 19
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- 239000003795 chemical substances by application Substances 0.000 claims description 14
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- 239000000203 mixture Substances 0.000 claims description 12
- 230000001376 precipitating effect Effects 0.000 claims description 12
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical group Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 12
- 229910002804 graphite Inorganic materials 0.000 claims description 11
- 239000010439 graphite Substances 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
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- INNSZZHSFSFSGS-UHFFFAOYSA-N acetic acid;titanium Chemical compound [Ti].CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O INNSZZHSFSFSGS-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000003599 detergent Substances 0.000 claims description 5
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- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 4
- 239000002041 carbon nanotube Substances 0.000 claims description 4
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 4
- 229910021389 graphene Inorganic materials 0.000 claims description 4
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 9
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- 230000000052 comparative effect Effects 0.000 description 6
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- KVFQMAZOBTXCAZ-UHFFFAOYSA-N 3,4-Hexanedione Chemical compound CCC(=O)C(=O)CC KVFQMAZOBTXCAZ-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
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- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 2
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- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
A porous composite metal catalyst for polyether synthesis and a preparation method thereof belong to the technical field of polyether metal catalysts. The catalyst is characterized by having a core-shell structure with a carbon material as a shell layer and an active core as a core, wherein the active core takes a compound of ortho-diketone and 1, 1-bis (diphenylphosphine) ethylene as an organic ligand and copper ions and titanium ions as active centers. The catalyst combines the advantages of metal catalytic activity and porous structure, has larger specific surface area and more active sites, and greatly improves the reaction rate and selectivity.
Description
Technical Field
The invention relates to a porous composite metal catalyst for polyether synthesis and a preparation method thereof, belonging to the technical field of polyether metal catalysts.
Background
Polyether synthesis is an important chemical reaction commonly used to prepare polymeric materials. In polyether synthesis, the metal catalyst may act as a catalyst, promoting the reaction and controlling the structure and properties of the polymer. Common catalysts include Lewis acids, acidic ionic liquids, transition metal catalysts, and the like. These metal catalysts can improve reaction rate, selectivity and product quality. In polyether synthesis, common metal catalysts include: acidic ionic liquid catalysts, lewis acid catalysts, transition metal catalysts, coordination polymer catalysts. These metal catalysts play a key role in polyether synthesis and can increase the reaction rate, control the polymerization degree and the product structure, thereby affecting the performance and the application of the polymer.
However, most of the existing catalysts have the defects of short service life, insufficient selectivity and the like. Such as titanium, zinc, zirconium and other transition metal catalysts which are commonly used at present are commonly used for catalyzing etherification reaction of ethylene oxide and glycerin. However, these transition metal catalysts often cause side reactions or by-product formation in applications, which can reduce product selectivity and affect synthesis efficiency and product purity.
Disclosure of Invention
The invention aims to solve the technical problems that: overcomes the defects of the prior art, and provides a porous composite metal catalyst for polyether synthesis with high selectivity and long service life and a preparation method thereof.
The technical scheme adopted for solving the technical problems is as follows: the porous composite metal catalyst for polyether synthesis is characterized by having a core-shell structure with a carbon material as a shell layer and an active core as a core, wherein the active core takes a compound of ortho-diketone and 1, 1-bis (diphenylphosphine) ethylene as an organic ligand and copper ions and titanium ions as active centers.
The catalyst belongs to MOF type catalyst and has excellent catalytic performance in polyether polyol synthesis. The invention takes the carbon material as a shell layer and takes the bimetal organic ligand as an active core, and the core-shell structure can reduce the external interference to the active core, thereby prolonging the service life of the catalyst. Copper ions and titanium ions serve as metal centers in the MOF structure and form coordination bonds with organic ligands, so that MOF crystals are promoted to be formed and participate in building a porous structure. Copper and titanium have good compatibility in chemical properties, and can effectively form a composite structure; the catalyst with double metal effect is obtained by compounding copper and titanium as active metal ions of a catalyst for polyether synthesis, and the catalyst has excellent catalytic performance, and particularly has better selectivity in epoxidation reaction between ethylene oxide and glycerin. The copper and titanium composite obtains synergistic effect, and improves catalytic activity and selectivity.
1, 1-Bis (diphenylphosphine) ethylene can provide additional coordination sites through phosphorus atoms to enhance the stability of copper and titanium metal ions. The selected ortho-diketone has two carbonyl groups, 1-bis (diphenyl phosphine) ethylene has two organic phosphine coordination sites, and the two organic ligands are double-tooth ligands, can form relatively stable metal complexes with copper ions and titanium ions, and are beneficial to regulating and controlling the structure of MOF. Preferably, in the porous composite metal catalyst for polyether synthesis, the molar ratio of the ortho-diketone to the 1, 1-bis (diphenylphosphine) ethylene is 100:50-150, and the molar ratio of the copper ion to the titanium ion is 10:1-4. The catalyst shows better polyether synthesis selectivity under the preferable proportion of copper ions and titanium ions.
In the porous composite metal catalyst for polyether synthesis, the vicinal diketone exhibits better selectivity for the mixed metal ion of copper ion and titanium ion than other types of ketone, and the vicinal diketone used may be 2, 3-butanedione, 2, 3-pentanedione, 2, 3-hexanedione, 3, 4-hexanedione, or the like, more preferably, the vicinal diketone is 2, 3-butanedione. The two carbonyl groups of the 2, 3-butanedione are close to each other, the molecular overall structure is smaller, the active sites formed by ligands with the same size are more, and the catalyst has stronger catalytic capability.
In the porous composite metal catalyst for polyether synthesis, the carbon material is used as a shell layer, so that the porous composite metal catalyst has good conductivity, and is beneficial to improving the electron transfer efficiency of the catalyst, thereby promoting the catalytic reaction. And the carbon material has higher chemical stability and inertness, so that the carbon material can keep stability under the catalytic reaction condition, and the service life of the catalyst is prolonged. Preferably, the carbon material is graphite, graphene or carbon nanotubes. The preferred carbon material can form stable pi-pi stacking with 1, 1-bis (diphenylphosphine) ethylene in the organic ligand, and can obtain a composite metal catalyst with more stable structure and higher strength; graphite is preferred, and the cost is lower.
The preparation method of the porous composite metal catalyst for polyether synthesis is characterized by comprising the following steps:
1) Adding ortho-diketone and 1, 1-bis (diphenylphosphine) ethylene into an organic solvent according to a proportion in a dry reactor, and uniformly mixing to obtain a ligand solution;
2) Then adding copper salt and titanium salt into the ligand solution according to the proportion, stirring and heating to uniformly mix;
3) Dripping a precipitating agent to promote the formation of composite metal catalyst crystals, controlling the reaction temperature at 50-55 ℃ and the dripping time of the precipitating agent at 7-10 h;
4) After the reaction is finished, cooling to normal temperature, continuously stirring, and directly adding a carbon material into the system, wherein the mass ratio of the total mass of copper salt and titanium salt to the carbon material is 1:8-10;
5) Washing with detergent, solid-liquid separating to obtain solid product, and drying.
The preparation method has simple process, basically does not need high-temperature conditions in the process, has low energy consumption and can prepare the porous composite metal catalyst for polyether synthesis with higher yield.
Most organic solvents miscible with alcohols may be used as solvents in the present invention. Preferably, in the above preparation method, the organic solvent in step 1) is Dimethylformamide (DMF).
Preferably, in the above preparation method, the copper salt in step 2) is copper chloride, copper acetate or copper sulfate, and the titanium salt is titanium tetrachloride or titanium acetate.
Preferably, in the above preparation method, the precipitating agent in step 3) is ethylene glycol or propylene glycol. Ethylene glycol or propylene glycol is used as a separating agent, so that the solubility can be well regulated, the crystal precipitation of the composite metal catalyst is promoted, and a stable shell layer is formed directly through pi-pi stacking after a carbon material is added.
Washing may be performed with low molecular alcohols or water. Preferably, in the above preparation method, the detergent in step 5) is methanol. Methanol is used as a detergent and is easy to dry and recycle.
Compared with the prior art, the porous composite metal catalyst for polyether synthesis and the preparation method thereof have the following beneficial effects: the invention combines the ortho-diketone and the 1, 1-bis (diphenyl phosphine) ethylene to regulate the structure of the catalyst, forms specific pore structure and surface property, is favorable for the catalytic reaction of polyether synthesis, promotes the interaction between two metal ions in two different types, possibly generates a synergistic effect, and improves the catalytic performance. The catalyst combines the advantages of metal catalytic activity and porous structure, has larger specific surface area and more active sites, and greatly improves the reaction rate and selectivity.
Detailed Description
The present invention will be specifically described below by way of examples. All materials are commercially available, unless otherwise indicated.
Example 1
1) Adding 2, 3-butanedione and 1, 1-bis (diphenylphosphine) ethylene into Dimethylformamide (DMF) according to the molar ratio of 100:100 in a dry reactor, and uniformly mixing to prepare a ligand solution with the total mass concentration of 35%;
2) Adding copper chloride and titanium tetrachloride into the ligand solution according to the molar ratio of 10:2.5, so that the total mass concentration of metal ions is 30%, stirring and heating to uniformly mix;
3) Dripping glycol to promote the formation of composite metal catalyst crystal, controlling the reaction temperature at 52 ℃, and controlling the dripping time of the precipitating agent at 8h;
4) After the reaction is finished, cooling to normal temperature, continuously stirring, and directly adding graphite into the system, wherein the mass ratio of the total mass of copper chloride and titanium tetrachloride to the graphite is 1:9;
5) Washing with methanol, solid-liquid separating to obtain solid product, and drying.
Example 2
1) Adding 2, 3-butanedione and 1, 1-bis (diphenylphosphine) ethylene into Dimethylformamide (DMF) according to a molar ratio of 100:125 in a dry reactor, and uniformly mixing to prepare a ligand solution with a total mass concentration of 32%;
2) Adding copper chloride and titanium tetrachloride into the ligand solution according to the molar ratio of 10:3, so that the total mass concentration of metal ions is 28%, stirring and heating to uniformly mix;
3) Propylene glycol is dripped to promote the formation of composite metal catalyst crystals, the reaction temperature is controlled at 53 ℃, and the dripping time of the precipitating agent is controlled at 8 hours;
4) After the reaction is finished, cooling to normal temperature, continuously stirring, and directly adding graphite into the system, wherein the mass ratio of the total mass of copper chloride and titanium tetrachloride to the graphite is 1:9;
5) Washing with methanol, solid-liquid separating to obtain solid product, and drying.
Example 3
1) Adding 2, 3-butanedione and 1, 1-bis (diphenylphosphine) ethylene into Dimethylformamide (DMF) according to a molar ratio of 100:75 in a dry reactor, and uniformly mixing to prepare a ligand solution with the total mass concentration of 38%;
2) Adding copper chloride and titanium tetrachloride into the ligand solution according to the molar ratio of 10:2, so that the total mass concentration of metal ions is 35%, stirring and heating to uniformly mix;
3) Dripping glycol to promote the formation of composite metal catalyst crystal, controlling the reaction temperature at 52 ℃, and controlling the dripping time of the precipitating agent at 8.5h;
4) After the reaction is finished, cooling to normal temperature, continuously stirring, and directly adding graphite into the system, wherein the mass ratio of the total mass of copper chloride and titanium tetrachloride to the graphite is 1:8.5;
5) Washing with methanol, solid-liquid separating to obtain solid product, and drying.
Example 4
1) Adding 2, 3-pentanedione and 1, 1-bis (diphenylphosphine) ethylene into Dimethylformamide (DMF) according to the molar ratio of 100:100 in a dry reactor, and uniformly mixing to prepare a ligand solution with the total mass concentration of 35%;
2) Adding copper acetate and titanium acetate into the ligand solution according to the molar ratio of 10:3, so that the total mass concentration of metal ions is 32%, stirring and heating to uniformly mix;
3) Dripping glycol to promote the formation of composite metal catalyst crystal, controlling the reaction temperature at 52 ℃, and controlling the dripping time of the precipitating agent at 8h;
4) After the reaction is finished, cooling to normal temperature, continuously stirring, and directly adding graphene into the system, wherein the mass ratio of the total mass of copper acetate and titanium acetate to the graphene is 1:9;
5) Washing with methanol, solid-liquid separating to obtain solid product, and drying.
Example 5
1) 3, 4-Hexanedione and 1, 1-bis (diphenylphosphine) ethylene are added into Dimethylformamide (DMF) according to the molar ratio of 100:100 in a dry reactor and uniformly mixed to prepare a ligand solution with the total mass concentration of 35%;
2) Adding copper chloride and titanium tetrachloride into the ligand solution according to the molar ratio of 10:2, so that the total mass concentration of metal ions is 32%, stirring and heating to uniformly mix;
3) Dripping ethylene glycol or propylene glycol to promote the formation of composite metal catalyst crystals, controlling the reaction temperature at 53 ℃, and controlling the dripping time of the precipitating agent at 8.5h;
4) After the reaction is finished, cooling to normal temperature, continuously stirring, and directly adding carbon nano tubes into the system, wherein the mass ratio of the total mass of copper salt and titanium salt to the carbon nano tubes is 1:9;
5) Washing with methanol, solid-liquid separating to obtain solid product, and drying.
Example 6
1) Adding 2, 3-butanedione and 1, 1-bis (diphenylphosphine) ethylene into Dimethylformamide (DMF) according to the molar ratio of 100:50 in a dry reactor, and uniformly mixing to prepare a ligand solution with the total mass concentration of 40%;
2) Adding copper chloride and titanium tetrachloride into the ligand solution according to the molar ratio of 10:1, so that the total mass concentration of metal ions is 35%, stirring and heating to uniformly mix;
3) Propylene glycol is dripped to promote the formation of composite metal catalyst crystals, the reaction temperature is controlled at 55 ℃, and the dripping time of the precipitating agent is controlled at 7 hours;
4) After the reaction is finished, cooling to normal temperature, continuously stirring, and directly adding graphite into the system, wherein the mass ratio of the total mass of the copper chloride and the titanium tetrachloride to the carbon material is 1:8;
5) Washing with methanol, solid-liquid separating to obtain solid product, and drying.
Example 7
1) Adding 2, 3-butanedione and 1, 1-bis (diphenylphosphine) ethylene into Dimethylformamide (DMF) according to a molar ratio of 100:150 in a dry reactor, and uniformly mixing to prepare a ligand solution with a total mass concentration of 25%;
2) Adding copper chloride and titanium acetate into the ligand solution according to the molar ratio of 10:4, so that the total mass concentration of metal ions is 20%, stirring and heating to uniformly mix;
3) Dripping glycol to promote the formation of composite metal catalyst crystal, controlling the reaction temperature at 50 ℃ and controlling the dripping time of the precipitating agent at 10h;
4) After the reaction is finished, cooling to normal temperature, continuously stirring, and directly adding graphite into the system, wherein the mass ratio of the total mass of copper chloride and titanium acetate to the carbon material is 1:10;
5) Washing with methanol, solid-liquid separating to obtain solid product, and drying.
Comparative example 1
The basic formulation and preparation process were the same as in example 1, except that an equimolar amount of 2, 5-hexanedione was used instead of 2, 3-butanedione.
Comparative example 2
The basic formulation and preparation process were the same as in example 1, except that the molar ratio of copper chloride to titanium tetrachloride was adjusted to 1:1.
Comparative example 3
The basic formulation and preparation process were the same as in example 1 except that only 1, 1-bis (diphenylphosphine) ethylene was used as the organic ligand and an equimolar amount of 1, 1-bis (diphenylphosphine) ethylene was used instead of 2, 3-butanedione.
The catalysts prepared in each example were used as catalysts in the process for preparing polyethers from ethylene oxide and glycerol, respectively, for testing the catalytic performance: ethylene oxide, glycerin and a catalyst are put into a high-pressure reaction kettle according to the mass ratio of 700:1:0.001; and (3) heating to the reaction temperature of 55 ℃ to react until phthalic anhydride is completely reacted for 6 hours, and washing and devolatilizing to obtain polyether.
The results of the performance test of the catalysts obtained in examples 1 to 7 are shown in Table 1. Catalyst life refers to the time from when the catalyst obtained in the examples was put into service to when the catalytic efficiency was lost by 30%, excluding the time for catalyst reactivation and re-put into service.
TABLE 1 Performance test results
| Catalyst compressive strength N/cm | Catalyst life h | Polyether yield% | |
| Example 1 | 78 | 489 | 99.7 |
| Example 2 | 78 | 476 | 99.6 |
| Example 3 | 77 | 478 | 99.4 |
| Example 4 | 79 | 483 | 99.5 |
| Example 5 | 76 | 480 | 99.4 |
| Example 6 | 73 | 457 | 99.2 |
| Example 7 | 72 | 461 | 99.1 |
| Comparative example 1 | 34 | 286 | 84.3 |
| Comparative example 2 | 77 | 367 | 73.4 |
| Comparative example 3 | 81 | 413 | 85.7 |
The above description is only a preferred embodiment of the present invention, and is not intended to limit the invention in any way, and any person skilled in the art may make modifications or alterations to the disclosed technical content to the equivalent embodiments. However, any simple modification, equivalent variation and variation of the above embodiments according to the technical substance of the present invention still fall within the protection scope of the technical solution of the present invention.
Claims (6)
1. A porous composite metal catalyst for polyether synthesis is characterized by comprising a core-shell structure taking a carbon material as a shell layer and an active core as a core, wherein the active core takes a compound of ortho-diketone and 1, 1-bis (diphenylphosphine) ethylene as an organic ligand and copper ions and titanium ions as active centers;
the molar ratio of the ortho-diketone to the 1, 1-bis (diphenylphosphine) ethylene is 100:50-150, and the molar ratio of the copper ions to the titanium ions is 10:1-4; the carbon material is graphite, graphene or carbon nano tube.
2. The porous composite metal catalyst for polyether synthesis according to claim 1, wherein the ortho-diketone is 2, 3-butanedione.
3. A method for preparing the porous composite metal catalyst for polyether synthesis according to claim 1 or 2, characterized by comprising the steps of:
1) Adding ortho-diketone and 1, 1-bis (diphenylphosphine) ethylene into an organic solvent according to a proportion in a dry reactor, and uniformly mixing to obtain a ligand solution;
2) Then adding copper salt and titanium salt into the ligand solution according to the proportion, stirring and heating to uniformly mix;
3) Dripping a precipitating agent to promote the formation of composite metal catalyst crystals, controlling the reaction temperature at 50-55 ℃ and the dripping time of the precipitating agent at 7-10 h; the separating out agent is ethylene glycol or propylene glycol;
4) After the reaction is finished, cooling to normal temperature, continuously stirring, and directly adding a carbon material into the system, wherein the mass ratio of the total mass of copper salt and titanium salt to the carbon material is 1:8-10;
5) Washing with detergent, solid-liquid separating to obtain solid product, and drying.
4. The method for preparing a porous composite metal catalyst for polyether synthesis according to claim 3, wherein the organic solvent in step 1) is dimethylformamide.
5. The method for preparing a porous composite metal catalyst for polyether synthesis according to claim 3, wherein the copper salt in the step 2) is copper chloride, copper acetate or copper sulfate, and the titanium salt is titanium tetrachloride or titanium acetate.
6. The method for preparing a porous composite metal catalyst for polyether synthesis according to claim 3, wherein the detergent in step 5) is methanol.
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